Stabilization of protein-containing textiles



United States Patent STABILIZATION OF PROTEIN-CONTAINING TEXTILESBenjamin B. Kine and Nathaniel A. Matlin, Levittown, Pa., assignors toRohm & Haas Company,'Philadelphia, Pa, a corporation of Delaware NoDrawing. Application March 22, 1954, Serial No. 417,979

Claims. (Cl. 117-141) This invention relates to the treatment ofprotein-containing textile materials and to the products thereof. It

relates more particularly to a process of treating textile materialscomprising scale-surfaced proteinfibers, such as wool andwool-containing fabric, whereby the textile materials are stabilizedagainst shrinking and felting.

An object of this invention is to provide aqueous dispersions of resinswhich are so stable that they can be stored and shipped, and which, whenthey are applied to protein-containing textile materials and are thenheated, markedly reduce the tendency of the materials to shrink orrender them substantially shrink-proof. Another object is to provide aprocess for shrink-proofing and feltproofing textiles containingscale-surfaced protein fibers, Whether of natural or artificial origin,through the use of the aforesaid dispersions. It is an object toshrink-proof and felt-proof the textiles without adversely affectingsuch other properties of the textile as wearing qualities, tensilestrength, or hand. Still another object is to produce protein-containingtextile materials, particularly woolen fabrics, which have :a muchreduced tendency to shrink and which also retain the desirablecharacteristics which are associated with woolen fabrics. A

While this invention is principally concerned with improvements of, andmore particularly the reduction of shrinkage and/or completestabilization of textile materials of proteinaceous types, and while theinvention is described primarily in terms of Wool-containing textiles,the invention embraces the treatment of other proteincontaining textilematerials, such as those made of or containing silk, mohair, fur, Aralacand other synthetic fibers which are produced from casein, soybeans,collagen, et cetera, and especially scale-surfaced protein fibers ofeither natural or artificial origin. The terms textile and tex tilematerials are used herein to include filaments, fibers, yarns, thread,plied yarns, rovings, and slivers'as such or in Woven, knitted, feltedor otherwise formed fabrics, sheets, cloths and the like. Such textilematerials may contain only one kind of proteinaceous fiber or a mixtureof such fibers with other natural or synthetic fibers, such as ofcotton, linen, rayon, nylon, or polymers of acrylonitrile.

A number of different methods have been proposed for the treatment oftextile materials formed of or containing Wool or other protein fibersin order to prevent or decrease felting and shrinking. In many cases,such reduction in felting and shrinking tendencies has been obtained atthe sacrifice of some other desirable property of the material.

Some treatments damage the fiber and reduce the wearing qualities whileothers impart an undesirable harshness to the fabric. Other-treatmentsare not permanently effective and may even cause an ultimate increase inshrinkage. Still other shrink-proofing methods are difficult to applywith uniformity and create hazards to the workers involved in theirapplications.

Certain polymers of the linear type have also been recommended, such asthose containing isocyanate groups and certain esters of acrylic ormethacrylic acid, such as the glycidyl esters thereof. The types ofpolymers of this class that have been found effective for reducing theshrinkage and felting of pntein-containing textiles have so far been ofrather limited scope. It has been found that many polymers of this type,which are quite similar to those which are effective have no effect orhave so little effect as to be of no practical value. For example,polymers or copolymers of glyceryl methacrylate,

CH2=C(CH3)COOCH2CH(OH) CHzOH are of this character.

The process of treating the textile materials in accordance with theinvention comprises impregnating them with an aqueous dispersion of thekind described in detail below and then heating the textiles at atemperature which isat least as high as 212" 'F., but which is lowerthan the charring point of the textile. During the treatment of thetextiles in this Way, a chemical reaction is believed to take placebetween the proteinaceous portion of the textile and the copolymer inthe dispersion. The copolymer appears to be chemically bound to thetextile and not merely deposited as a dry coating on the fibers. As aresult, the resinous copolymer is not leached or removed from thetextile during subsequent wet-Washing or drycleaning operations.

In accordance with the present invention, it has been found thatpolymers of certain ethers and sulfides which contain a single terminalalcoholic hydroxyl group on the monomeric units of the polymer arecapable of improving the abrasion resistance of protein-containingtextiles and are highly effective for the stabilization of textilescomprising scale-surfaced protein fibers, such as Wool. Morespecifically, it has been found that marked reduction in the shrinkingand felting properties of Wool-containing textiles can be obtained bythe application thereto of an aqueous dispersion of a water-insoluble,linear polymer of at least 3% by weight in the polymer molecule, of amonoethylenically unsaturated monomeric compound having the followinggeneral formula:

CH2=CH AROH where A is O or S-, and R is a straight or branched chainalkylene group having fro-m 2 to 10 carbon atoms, C2H4AC2H4,C2H4N(R)C2H4-, or C2H4N(R (R (X)C2H4 where R is H, CH3, C2H5,

f or C2H4OH and R and R are methyl, ethyl, or hydroxyethyl(.CzH4OH)groups and X is a negative radical, such as OH, Cl, Br, I, CH3SO4, andtolyl sulfonate. A preferred group isthat of the ethers having theformula:

CH2=CH-O( CH2 a:OH

where x may be 2 to 10 but is preferably 3 to 6, the efiiciencygenerally beinglat a maximum when x is 5.

Examples of these monomers are:

Thiodiglycol monovinyl sulfide Diethyleneglycol monovinyl ether Thehigher hydroxyalkyl vinyl ethers may be made in the same way as thelower ones are by the Reppe processesdisclosed in various patents andpublications.

The polymers must not be water-soluble. Where the hydroxy ether orhydroxy sulfide monomer that is polymerized is of such character that ahomopolymer produced therefrom is appreciably water-soluble, it isnecessary to copolymerize such a monomer with at least one othercopolymerizable monoethylenically unsaturated monomer which is of acharacter that will render the final copolymer insoluble in water. Manyof the hydroxyl-containing monomers have such a large proproportion ofhydrophobic groups in their molecule that homopolymers thereof willnecessarily be water-insoluble and in such cases, a homopolymer can beapplied to the fabrics for accomplishing the purpose of the invention.Frequently, however, it is preferable from the cost standpoint tocopolymerize the hydroxy monomer with a cheaper and more readilyavailable comonomer. Preferred compositions of the invention are,therefore, those copolymers of from 3 to 30% of the hydroxyl-containingether or sulfide monomer or of :1 mixture of such monomers, the balanceof the copolymer being formed of other less expensive comonomers.

Other polymerizable compounds containing a single ethylenicallyunsaturated group that may be copolymerized with the ethers or sulfidesto produce binary, ternary, etc. coploymers include the esters ofacrylic acid or methacrylic acid with monohydric alcohols such asmethyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl,phenylethyl, and the like; diesters of itaconic acid and the abovealcohols; esters of maleic, fumaric or citraconic acids, and the abovealcohols; vinyl esters of carboxylic acids such as acetic, propionic,butyric, and the like; vinyloxyalkyl esters such as vinyloxyethylacetate, etc.;vinyl ethers such as ethyl vinyl ether, butyl vinyl ether,octyl vinyl ether; methacrylonitrile or acrylonitrile; acrylamide, ormethacrylamide, and N-alkyl-substituted amides of these types;vinyltoluene, vinylnaphthalenes, such as 4-chloro-l-vinylnaphthalene,vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride,vinyli-dene cyanide, l-chloro-l-fiuoroethylene, ethylene, and styrene.

The emulsifiers or dispersingagents that may be used for preparing themonomeric emulsions before copolymerization or dispersions of thepolymer after polymerization are preferably of the non-ionic type andinclude the following: alkylphenoxypolyethoxyethanols having alkylgroups of about seven to eighteen carbon atoms and 6 to 60 or moreoxyethylene units, such as heptylphenoxypolyethoxyethanols,octylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols,nonyl phenoxypolyethoxyethanols, dodecylphenoxypollyethoxyethanols, andthe like; polyet-hoxyethanol derivatives of methylene linked alkylphenols; sulfur-containing agents 7 such as those made by condensing 6to 60 or more moles of ethylene oxide with nonyl, dodecyl, tetradecyl, tdodecyl, and the like mercaptans or with alkylthiophenols having alkylgroups of six to fifteen carbon atoms; ethylene oxide derivatives oflong-chained carboxylic acids, such as lauric, myristic, palmitic,oleic, and the like, or mixtures of acids such as found in tall oilcontaining 6 to 60 oxyethylene units per'molecule; analogous ethyleneoxide condensates of long-chained alcohols, such as octyl, decyl,lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified oresterified polyhydroxy compounds having a hydrophobic hydrocarbon chain,such as sorbitan monostearate containing 6 to 60 oxyethylene units,etc.; also ethylene oxide condensates of long-chain or branched-chainamines, such as dodecylamine, hexadecylamine, and octadecylamine,containing 6 to 60 oxyethylene groups; block copolymers of ethyleneoxide and propylene oxide comprising a hydrophobic propylene oxidesection combined with one or more hydrophilic ethylene oxide sections.

Particularly valuable resin dispersions are obtained by emulsifying amixture of (a) one or more of the ethers or sulfides above and (b) oneor more monomeric esters of acrylic, methacrylic, or itaconic acid ormixtures of these acids in water and polymerizing the mixture while itis in the emulsified form. The monomeric esters which have proven to bemost satisfactory are the alkyl esters in which the alkyl group containsone to eight carbon atoms and which are exemplified by the following:methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl,tert-butyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, and Z-ethylhexylacrylates, methacrylates, and itaconates.

The polymerizable emulsions can be prepared at temperatures from 0 C. toabout 100 C., but intermediate temperatures are much preferred. Thus,when the preferred copolymers with esters are made with the esters inwhich the alkyl group contains one to four carbon atoms, a temperaturefrom about 10 C. to about 60 C. is employed whereas a highertemperature; e. g., 30 C. to C., is recommended when esters containingfive to eight carbon atoms in the'alkyl group are copolymerized.Peroxidic free-radical catalysts, particularly catalytic systems of theredox type, are recommended. Such systems, as is well known, arecombinations of oxidizing agents and reducing agents such as acombination of potassium persulfate and sodium metabisulfite. Othersuitable peroxidic agents include the per-salts such as the alkali metaland ammonium persulfates and perborates, hydrogen peroxide, organichydroperoxides such as tert-butyl hydroperoxide and cumenehydroperoxide, and esters such as tert-butyl perbenzoate. Other reducingagents include water-soluble thiosulfates, tertiary amines, such astriethanolamine, hydrosulfites, and the salts, such as the sulfates, ofmetals which are capable of existing in more than one valence state suchas cobalt, iron, nickel, and copper. The most convenient method ofpreparing the dispersions of copolymers comprises agitating an aqueoussuspension or emulsion of a mixture of copolymerizable monomers and aredox catalytic combination at room temperature without the applicationof external heat. The amount of catalyst can vary but for purposes ofefliciency from 0.01% to 3.0%, based on the weight of the monomers, ofthe peroxidic agent and the same or lower proportions of the reducingagent are recommended. In this way, it is possible to preparedispersions which contain as little as 1% and as much as 60% or evenmore of the resinous copolymer on a weight basis. It is, however, morepractical, and hence preferred, to produce dispersions which containabout 30-50% resin-solids.

The proportion of the polymer that is applied to the fabric may varywidely, such as from 1 to 20% by weight of the fabric, a proportion of 3to 7 /z% being preferred. The hand or feel of the fabric may be variedwidely depending on the polymer selected. Thus polymers of ethers whichcontain a long-chain alkylene group between the terminal hydroxyl andthe ether oxygen will generally have a softer hand than those with ashorter alkylene chain. The same applies when sulfide monomers areemployed. The variation in hand may be controlled by the selection ofthe comonomer as well. Thus, for a given sulfide or ether monomercontaining terminal hydroxyl groups, a softer and more lubricous handmay be imparted by copolymerizing with a comonomer or such characterthat it introduces long-chain fatty groups into the copolymer. Forexample, the hydroxylgroup-containing monomer may be copolymerized withacrylic, methacrylic, or itaconic esters of alcohols containing from 1to 18 carbon atoms, the longer the chain of the alcohol, the morelubricous the hand.

The dispersion is deposited on the textile material by such means asexhausting, spraying, or dipping. What is required is that the textilematerial be saturated and impregnated by the dispersion. This can bedone at any desired temperature short of the boiling point of thedispersion. Ordinarily the textile is padded at room temperature with adispersion which has been adjusted to a resin-content of about 1% to25%. The material being treated must pickppxor take upandptheniretainsuflicient dispersions to providefrom 1% to about 20%,'and'preferably from 3% to 74/2% of the copolymer, based on the weightof the-dry textile.

The impregnated textile material must then be heated at .a temperaturebetween 212 F. and 400 F. for a period of about one-half'minute to 30minutes, the higher the temperature, the shorter the period required. Aflash cure at temperaturesabove 400 F., even up to 700 F. for shortperiods of five to ten seconds, may be employed. In any event, the timeand temperature should not be such as to damage the fabric. Preferablythis heating is efiectedat aqtemperature from 240 F. (for about 1-0l5.minutes) .t0.about13.10 F. .(for about 5-10 minutes'), .andjitisbelieved ithat it effects some chemical reaction involving thepolymerand possibly the textile. In

anyevent, the, heating sets thepolymer on the textile, and

in the case of wool, reduces shrinkage and/or imparts full dimensional:stability thereto. Drying .of the treated textile and the .heattreatment which .eflfects the chemitcal reaction -.can be carried outsimultaneously or. concurrently in one step, or theiextile can .besubstantially or completely dried at a conveniently lower temperatureand then heated later at the higher temperature. As will .be evident'toathose skilled -.in the art,-the optimal-length ftheheatingperiod-depends on the;particular temperature which :isemployed, :on the particular -copoiymer,

. andon the-quantity thereof which is on the textile. But

' ily determinedby heating pieces of theirnpregnated textile for=varying lengths of "time at a (given temperature and then measuring theresultant stabilization of the individual pieces by means of awet-washing test.

In-sornecases, it may be advantageous toad'd an acid tothedispersionwith which the textile is treated to accelerate the reaction and tobring about the stabilization or reduction in shrinkage "in'a shorterperiod of time at a. given temperature or atadower temperature ina,given time. .Strong ac'idssuch as formic, oxalic, .sulfuric, .andphosphoric acids are recommended. For *this purpose from 1.% to 12%.acid,-.based on the weight .of the pad liquor, is suggested. It hasalso been found that the use in conjunctionwith the dispersions of .such.acid catalyst with .an auxiliary reactive substance, .such (asformaldehyde, or materials which are equivalents of formaldehyde suc'hasg'lyoxal 0r 'formals,-or mixtures .ofiormaldehyde or the like withaminoplast-forming compounds, or low-molecular weight, .waterasolub'le,reaction products, preferably of formaldehydeor the like with suchcompounds-enhances the stabilization of'wool'en or pro- While suchauxiliary reactive -subteina'ceous textiles. stances and the acidcatalyst may be "employed as an added component -of--the dispersions,they may'also be employed-by applying-a solution of the auxiliaryreactive substance and theacid catalyst'after the textile'has'beentreatedwith the dispersion. The use :o'ftheauxiliary reactive substanceis advantageous in some cases where it-becomes especially evidentonextended laundering of the textile. Also in combination fabrics, such asthose containing fibers or yarns'of .silk or cellulosic type, such ascotton or rayon, as Well as fibers or yarns of proteinaceeus types, such.as wool, including :as an example rivatives thereof, such as N,N-ethyleneurea, N,N-ethyleneurea, N,N'-dimethylurea, NN'-diethylurea,N,N'-dimethoxymethylurea, -N,N-d-imethoxymethylurea, N,N-.diethoxyethylurea, tetramethoxymethylurea, tetraethoxyethylurea.Similar reaction ;products of formaldehyde with: triazines, :such .asmelamine may also be: employed, .such as N,N-'dimethylmelamine andalcohol-modified melamine-formaldehyde thermosetting resin condensatese. g., of methyl and ethyl alcohols, for example,dimethoxymethyl-monomethylolmelamine.

The treated textiles are characterized bygreater resistance to abrasionand/ or reduced shrinkage and, in many cases, fully practicaldimensional stability against laundering, by which is meant "that theyare substantially shrink-proof. They do not stiffen, degrade or discoloron aging -or on exposure to ultraviolet light as do ,comparable textileswhich have been treated, for example, with laticesof butadienecopolymers.

The effectiveness of the dispersions exemplified below in stabilizingwool 'wasdetermined by impregnating measured pieces of flannel withthem, drying, and heating the impregnated pieces of flannel-atetemperature of 240 F. or higher, laundering thepieccs in hot water, thendrying "them and measuringtheshrinkage. In these tests pieces of 'Botany.woolenflannel (style #405;.2/2 right hand 45 twill, 5'5 x 44; Setwist.in ends, Z in picks;

scoured, carbonized, neutralized .and bleached) were used. Allpieceswere 10 inchessquare, with axesalong the yarn systems. The piecesof flannel were padded with a pad liquor of thexresin dispersion whichwas so adjusted .in solids-content ,as to provide the desired amountofresins-solids ,(.1-%'2i0% based on the weight of the ,dry flannel) at-,a pick-up of about that is,

:at a temperature of at least 240 F. The specimens werewashed,*togetherwith-untreated pieces of flannel, in

a Cascade wheel washer containing '70 grams of soap :(Ivory) in 10gallons of water for five hours. In all :cases the loadin the washer wasmade up to threepounds with :cotton towe'ling and the temperature wasmaintained at 140 F. The values of shrinkage are given as percentagereduction in the initial area after taking into account any inherentresidual shrinkage in the initial fabric that may be presentasraresult=of previous drying under tension and is achievable by-simplywetting and drying. In other words, the shrinkage values hereinbelow areobtained by subtracting relaxation shrinkage fromthe. actual shrinkagemeasured.

The following examples serve to illustrate this invention:

Example 1 A dispersion of a copolymer was prepared by emulsifying partsby weight of.n-butyl acrylate with l0 parts 'by weightof 8-hydroxyethylvinyl sulfide in about 300 ,pa-rtsby'weight of waterv with about v6parts by weight of an ethylene oxide condensation product of an octylphenol containing between 30 and 50 oxyethylene units per molecule. Tothe emulsified monomers 0.3% by weight (on the total Weight-of monomers)of ammonium persult'ate, 1.0% of triethanolamine, and 0.06% of sodium.h-ydrosulfite were added locatalyze 'the-copolymerization which .was.carried -out for a period of seventeen minutes. lldringwthis period thetemperature rose from 20 C. to 46 C.

The resin dispersion was'diluted to a 10% concentration. of the resin(copolymer) content and applied .to a woolfiannel as described above.After dryinglO minutes at 240 F., foliowedby curing for 10 minutesat 300F., it was found that .the proportion vof copolymer applied to thefabric was about 7.5% of the weight of the fabric. The shrinkage of thetreated .f-abric after the five-hour wash described hereinabove waszero.

Example 2 The procedure of Example 1 was followed except that only 7.5%of a copolymer of 95% of n-butyl acrylate and of fi-hydroxyethyl vinylsulfide were applied to the fabric. After the five-hour wash test, thefabric showed a shrinkage of 6%. A control fabric (untreated) showed 63%shrinkage after washing under the same conditions.

Example 3 The procedure of Example 2 was followed except that afterdrying the fabric at 240 C., it was passed through an aqueous solutioncontaining 1% sulfuric acid and 1% formaldehyde and then dried minutesat 240 C. and cured for a period of 10 minutes at 300 F. The resultingfabric showed no shrinkage after the five-hour wash test. Whereas thehand obtained in Example 1 was softer than that of the initial fabric,the formaldehyde treatment reduced the softness of the hand onlyslightly as compared to the product of Example 1.

Example 4 An aqueous dispersion was prepared of a copolymer of 95 partsby weight of n-butyl acrylate with 5 parts by weight of 'y-hydroxypropylvinyl sulfide. The procedure of Example 2 was followed and the shrinkageafter a fivehour wash was found to be 19% as compared to a 63% shrinkageof a control fabric after the five-hour wash test.

Example 5 The procedure of Example 3 was followed with the copolymer ofExample 4. The resulting formaldehydetreated fabric had a shrinkage of3% after the five-hour wash test.

Example 6 The procedure of Example 2 was followed with an aqueousdispersion of a copolymer of 95% by weight of n-butyl acrylate and 5% byweight of j8-hydroxyethyl vinyl ether. The fabric showed a shrinkage of22% after the five-hour wash which compared favorably with the controlfabric which shrunk 63% after the wash test.

Example 7 The procedure of Example 3 was followed with the copolymer ofExample 6. The fabric showed a shrinkage of 4% after the five-hour washtest.

Example 8 The procedure of Example 3 was followed with a copolymer ofExample 8. The formaldehyde treatment altered the hand only slightly anddid not affect the shrinking which amounted to zero after the five-hourwash.

Example 10 The procedure of Example 2 was followed with an aqueousdispersion of a copolymer of 85% s-butyl acrylate with of B-hydroxyethylvinyl ether. After the five-hour wash test, the fabric exhibited only 3%shrinka Example 11 The procedure of Example 3 was followed with the co-8 polymer of Example 10 and the resulting fabric showed no shrinkageafter the five-hour wash test.

Example 12 The procedure of Example 2 was followed with an aqueousdispersion of a copolymer of methyl methacrylate and 10% of6-hydroxyhexyl vinyl ether. The fabric obtained showed a shrinkage ofzero after the fivehour wash test. Both before and after the wash, thefabric had a sandy feel or hand and was of reduced luster as compared tothat of the initial fabric.

Example 13 The procedure of Example 1 was followed with a copolymer ofby weight of n-butyl acrylate with 5% by weight of diethylene glycolmonovinyl ether. The fabric showed no shrinkage after a five-hour washand both before and after the wash, it had an exteremely soft hand.

A similar copolymer containing 5% thiodiglycol monovinyl ether insteadof the diethylene glycol monovinyl ether when only 5% was applied to thefabric showed 1.9% shrinkage after the wash test.

Example 14 The procedure of Example 1 was followed with a copolymer of92% by weight of diethyl itaconate with 8% of S-hydroxyoctyl vinylether. The fabric obtained showed a shrinkage of zero percent after thefive-hour wash and it was characterized by an extremely soft lu- Example15 The procedure of Example 2 was followed with an aqueous dispersiondiluted to 20% resin-content of a copolymer of 97% of ethyl acrylatewith 3% of S-hydroxypentyl vinyl ether. The fabric after the five-hourwash test showed a shrinkage of 2%.

In the following examples, the nitrogen-containing polymers increasedthe capacity to take up many acid dyes.

Example 16 The procedure of Example 1 was followed with an aqueousdispersion of a copolymer of 95% n-butyl acrylate with 5% ofB-hydroxyethylaminoethyl vinyl ether. The fabric obtained showed ashrinkage of zero after a five-hour wash.

The same procedure is carried out with a copolymer of 60% ethylacrylate, 30% N-butyl methacrylamide, and 5% of the same ether. Thefabric shows a somewhat stiffer hand and no shrinkage on washing.

Example 17 The procedure of Example 1 was followed with a copolymer of95% n-butyl acrylate with 5% of N-fi-hydroxyethyl-N-methylaminoethylvinyl other except that the dispersion was diluted to about 2% and only1.5% of the copolymer was applied to the fabric. The treated fabricshowed no shrinkage after the five-hour wash test.

The same procedure was followed with a copolymer of 20% styrene, 70%ethyl acrylate and 10% of the same ether. The fabric had a somewhatstiffer hand but showed no appreciable shrinkage on washing.

Example 18 The procedure of Example 1 was followed with a copolymer ofabout 95% n-butyl acrylate with about 5% ofhydroxyethyldimethyl(vinyloxyethyl)ammonium hydroxide except that thedispersion was diluted to about 4.5% and only 3.5% of the copolymer wasapplied to the fabric. The treated fabric showed no shrinkage after thefive-hour wash test.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

rated monomeric units comprising at least 3% by weight,

in the polymer molecule, of units of a monomer having the formulaCH2=CH'A--ROH where A is selected from the elements and S, and R isselected from the class consisting of straight and branched chainalkylene groups having from 2 to carbon atoms, -C2H4AC2H4,C2H4N(R')C2H4- and C2H4N(R (R )(X)C2H4- where R is selected from thegroup consisting of H, methyl, ethyl, and C2H4OH, R and R are selectedfrom the group consisting of methyl, ethyl, and C2H4OH, and X is anegative radical.

2. A composition for the treatment of protein-containing textilematerials comprising an aqueous dispersion of a water-insoluble polymerof at least 3% by weight, in the polymer molecule, of a monomer havingthe formula where x is an integer having a value from 2 to 10.

3. A composition for the treatment of protein-containing textilematerials comprising an aqueous dispersion of a water-insoluble polymerof at least 3% by weight, in the polymer molecule, of a monomer havingthe formula where x is an integer having a value from 2 to 10.

4. As an article of manufacture, a textile material comprising proteinfibers carrying from 1% to of a polymer of at least 3% of a monomerhaving the formula where A is selected from the elements 0 and S, and Ris selected from the class consisting of straight and branched chainalkylene groups having from 2 to 10 carbon atoms,

where R is selected from the group consisting of H, methyl, ethyl, andC2H4OH, R and R are selected from the group consisting of methyl, ethyl,and -C2H4OH, and X is a negative radical.

5. As an article of manufacture, a textile material comprising proteinfibers carrying from 1% to 20% of a water-insoluble polymer of at least3% of a monomer having the formula where x is an integer having a valuefrom 2 to 10.

6. As an article of manufacture, a textile material comprising woolfibers carrying from 1% to 20% of a waterinsoluble copolymer of 3% to of(1) a monomer having the formula where A is selected from the elements 0and S, and R is selected from the class consisting of straight andbranched chain alkylene groups having from 2 to 10 carbon atoms,

and

and

10 insoluble polymer of at least 3% of (N-fl-hydroxyethyl-N-methyl)aminoethylvinyl ether. i

8. As an article of manufacture, a textile material comprising woolfibers carrying from 1% to 20% of a waterinsoluble polymer of at least3% of hydroxyethyldimethyl(viny loxyethyl)ammonium hydroxide.

9. As an article of manufacture, a textile material comprising woolfibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3%of diethylene glycol monovinyl ether.

10. As an article of manufacture, a textile material comprising woolfibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3%of S-hydroxypentyl vinyl ether.

11. As an article of manufacture, a textile material comprising woolfibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3%of B-hydroxyethylaminoethyl vinyl ether.

l2. A process for treating proteinaceous textile materials to reduce theshrinkage thereof comprising treating such a material with an aqueousdispersion of a waterinsoluble polymer of at least 3% by weight, in thepolymer molecule, of a monomer having the formula where A is selectedfrom the elements 0 and S, and R is selected from the class consistingof straight and branched chain alkylene groups having from 2 to 10carbon atoms, -C2HAC2H4-, C2H4N(R)C2H4 and C2H4N(R (R (X)C2H4- where Ris selected from the group consisting of H, methyl, ethyl, and -C2H4OH,R and R are selected from the group consisting of methyl, ethyl, and-C2H4OH, and X is a negative radical, drying and heating the treatedtextile at a temperature of 212 F. to 700 F. for a period of about 5seconds to about 30 minutes but insufiicient to damage the fabric.

13. The process of claim 12 in which the polymer is a copolymer of(N-B-hydroxyethyl-N-methyl)aminoethyl vinyl ether with butyl acrylate.

14. The process of claim 12 in which the polymer is a copolymer ofhydroxyethyldimethyl(vinyloxyethyl)- ammonium hydroxide with butylacrylate.

15. The process of claim 12 in which the polymer is a copolymer ofdiethylene glycol monovinyl ether with butyl acrylate.

16. The process of claim 12 in which the polymer is a copolymer ofS-hydroxypentyl vinyl ether with butyl acrylate.

17. The process of claim 12 in which the polymer is a copolymer offi-hydroxyethylaminoethyl vinyl ether with butyl acrylate.

18. A process for treating proteinaceous textile mate rials to reducethe shrinkage thereof comprising treating such a material with anaqueous dispersion of a waterinsoluble polymer of at least 3% by weight,in the polymer molecule, of a monomer having the formula where A isselected from the elements 0 and S, and R is selected from the classconsisting of straight and branched chain alkylene groups having from 2to 10 carbon atoms, C2H4AC2H4, C2H4N(R')C2H4- and -C2H4N(R (R (X)C2H4--where R is selected from the group consisting of H, methyl, ethyl, andC2H4OH, R and R are selected from the group consisting of methyl, ethyl,and C2H4OH, and X is a negative radical, drying the textile, thentreating the textile with formaldehyde and an acid catalyst, and dryingand heating the treated textile at a temperature of 212 F. to 700 F. fora period of about 5 seconds to about 30 minutes but insufiicient todamage the fabric.

19. The process as defined in claim 18 in which the polymer is acopolymer of diethylene glycol monovinyl ether with butyl acrylate.

20. The process as defined in claim 18 in which the 1 1 polymer is a'copolymer of S-hydroxypentyl vinylether 2,477,218 with butyl acrylate.2,563,586 2,633,460 References Cited in the file of this patent UNITEDSTATES PATENTS 5 1,959,927 Reppe May 22, 1934 2,160,375 Voss et a1 May30, 1939 2,329,622 Johnstone, Jr., et a1. Sept. 14, 1943 12 ThompsonJuly 26, 1949 'Dazzi Aug. 7, 1951 Neher et a1 Mar. 31, 1953 OTHERREFERENCES Vinyl and Re1ated Po1ymer's, by Schildknecht, Copr. Feb. 20,1952, pages 615 to 619 relied on.

12. A PROCESS FOR TREATING PROTEINACEOUS TEXTILE MATERIALS TO REDUCE THESHRINKAGE THEREOF COMPRISING TREATING SUCH A MATERIAL WITH AN AQUEOUSDISPERSION OF A WATERINSOLUBLE POLYMER OF AT LEAST 3% BY WEIGHT, IN THEPOLYMER MOLECULE, OF A MONOMER HAVING THE FORMULA